Advanced Nanoscience and Technology: An Internation al Journal (ANTJ), Vol. 2, No.

1, March 2016

A NOVEL PRECURSOR IN PREPARATION AND

CHARACTERIZATION OF NICKEL OXIDE (NIO)
AND COBALT OXIDE (CO3O4) NANOPARTICLES
(NPS)VIA AQUEOUS CHEMICAL GROWTH
(ACG) TECHNIQUES
A.R Junejo1, S.Memon1, S.Pathan2
1

Institute of Information and Communication Technology, University of Sindh Jamshoro,

2
Center of Excellence and Analytical chemistry, University of Sindh Jamshoro

Abstract
Synthesis of Nickel Oxide (NiO) nanoparticles and cobalt oxide (CO3O4) materials synthesis by aqueous
chemical growth (ACG) Techniques. Oxide based material having a wide band gap, and suitable for
optical devices,Optoelectronic devices, UV photodetector, and Light emitting diode LEDs. The analysis
and characterizationof Nickel Oxide (NiO) and cobalt oxide (CO3O4) nanoparticles by(1) X-ray
diffraction (XRD), (2) Scanning electron microscopy (SEM), and (3) Ultravioletvisible (UVVis)
spectroscopy.

Key words
Nickel Oxide (NiO),Cobalt oxide (CO3O4), an oxide materials, Nanostructures.

1. INTRODUCTION
Challenging to find new Nano material focus on Metal oxide due to their special characteristics.
Due to accomplished CMOS process and unique properties of the material, Silicon has dominated
the semiconductor device industry since 1960s [2]. However less mobility and low band-gap
(lower breakdown voltage) of silicon limits the current carrying and output power generation
capability of traditional silicon based devices. Therefore compound semiconductors have become
the dominant materials for the applications like Light Emitting Diodes (LEDs), Laser Diodes
(LDs) and Radio Frequency (RF) devices. In this standpoint the typical III-V compound
semiconductors successfully get their place in semiconductor device industry especially in the
field of optoelectronic due to their significant properties such as wide band gap, High electron
mobility and wide spectral range.Metal oxides are dynamically used in the semiconductor
industry, such as most of the chips used in computers contain an oxide component. The synthesis,
characterization and applications of the metal oxide nanomaterials become challenging day by
day among researchers because of many unique features associated with nanometer size of the
particles [3-5].Among many wide band gap semiconductors such as NiO, ZnO, SiC, GaN, etc.,
ZnO as n-type material came under the scientific spotlight due to its distinguished execution in
fields like electronics, optics and photonics. Among various p-type materials, NiO is a promising
material having a wide band gap (3.6 eV to 4.0 eV) which is suitable for optical devices. NiO has
also been studied widely for applications in transparent conductive films, electrochromic devices
and heterogeneous catalysts along with lithium-ion batteriesand chemical sensors [6- 9]. and high
adsorption capability pave the way to make desirable surroundings for the immobilization of
biomolecule and bettered bio-sensing features [1013]. Therefore it is of great importance to
select that metal oxide nanostructure, which favors most the immobilization of the biomolecules.
Beside this they are very economical, less toxic and have great flexibility in
structures/morphology. Among the reported transition metal oxides, the cobalt oxide (Co 3O4) has
shown a lot of promise.
In the present work NiO and Co3O4 and their composite nanostructures have been synthesized and
used for device fabrication in different fields.And the main Objective Growth of NiO
nanostructures NiO has been used as p-type material due to its potential role in luminescence
applications along with its In this study NiO nanostructures have been developed. Cobalt
oxidenanostructures are synthesized by hydrothermal technique, which are investigated for their
luminescence properties.

DOI: 10.5121/antj.2016.2101

Advanced Nanoscience and Technology: An Internation al Journal (ANTJ), Vol. 2, No. 1, March 2016

2. RELATED WORK
The synthesis, characterization and applications of the metal oxide nanomaterials become
challenging day by day among researchers because of many unique features associated with
nanometer size of the particles [3, 4]. Generally the size of the particle has influence on the
properties in two aspects.
i.
ii.

Change in structural characteristics, such as the lattice symmetry and cell parameters.
Due to the oxygen vacancies in oxide nanoparticles atomic arrangement of the
materials varies from that in the bulk, along with occupation of electronic states
above the valance band. In addition to this an enhancement in the chemical activity of
the system also arises.

These properties of nanostructured oxides opened a door for applications Moreover, these
materials can be further functionalized by surface and structure modification. The good thermal
and chemical stability of these inorganic materials enable them to be widely used.Properties of
Nickle Oxide (NiO) . Some important application of nickel oxide in large scale optical switching
glazing, anti-ferromagnetic material, electrochromic display devices, lithium ion batteries (battery
cathode) and functional layer material for gas chemical sensors, catalysis andelectro chromic
films a[1-5].

Figure 1.Shows the face centered cubic (fcc) crystal structure of NiO. (Reproduced)

Semiconducting Propertiesof NiO thin film is nearly transparent, wide band-gap semiconductor,
and nonstoichiometric which shows p-type semiconductor conducting behavior [1,2, 9]. NiO
(Nickelous oxide) nanoparticles is an important metal oxide with a wide band gap of about 3.8
eV, acts as a P-type semiconductor and can be used as an emitter of 341nm, Properties of Cobalt
Oxide (Co3O4)semiconducting, capacitive characteristics and environmental friendliness. There
are two types of stable oxide of cobalt known as (CoO) and Co3O4, both of them are stable at
room temperature. Cobalt (II, III) oxides are inorganic and mixed valence compound[15].

Figure 2. The unit cell structure of Co3O4.(Reproduced)

Co3O4 is magnetic p-type semiconductor material with direct band gaps of 1.48 and 2.19ev,
however 1.6 ev is also reported in literature. Co3O4 is extensively used as catalyst, solid state
sensors, in pigment, electrochromic devices, solar energy absorber magnet and capacitor [15,
16].Cobalt oxides get much attention in past few years due to its capacitive characteristics
In present study we are interested to investigate the Luminescence properties of cobalt oxide to
use it as low power LEDs.

Advanced Nanoscience and Technology: An Internation al Journal (ANTJ), Vol. 2, No. 1, March 2016

3. SYNTHESIS TECHNIQUES
Synthesis is the back bone for the growth of nanostructures. In order to discover novel physical
properties and to realize possible applications of nanostructures and nanomaterials, the first
corner stone in nanotechnology is to fabricate and process nanomaterials and nanostructures at
their particular scale to achieve the best results. Mainly there are two approaches used for the
synthesis of nanomaterials according to the growth process.

Top down approach

Two approaches of synthesis techniques

Bottom up approach

Fig.no. 3. Basic synthesis techniques

3.1 Hydrothermal Synthesis.

Hydrothermal Synthesis orAqueous chemical growth (ACG) is a common and simple, low
temperature growth technique. Hydrothermal synthesis involves crystallizing materials from high
temperature aqueous solutions under autogenous pressure. Hydrothermal synthesis was typically
carried out in a steel pressure vessel known as an autoclave. Within the autoclave a temperature
gradient is established and maintained at the opposite ends of the growth chamber such that the
hotter end aids dissolution and the cooler end aids crystal growth[7, 3].
A precursor solution is required for the growth of NiO nanostructures as described earlier in this
method. Seeded substrates were attached to a Teflon sample holder and dipped into the precursor
solution for incubation at a temperature of 90 - 95C for 5 - 6 hours. The ACG method was used
for the growth of NiO nanostructure. A piece of substrate around 1 cm 2 cm in size was
cleaned by the standard cleaning procedure as described earlier. Then NiO nanoparticles (seeds)
solution was deposited on the substrate by using spin coater at a speed of 4000 rpm. This process
was repeated three times to achieve homogeneous and dense seed layer on the surface of the
substrate and then it was heated for several minutes for getting good adhesion of nano particles on
the surface of substrate. Now the sample was attached to the sample holder and immersed into the
precursors solution, which was prepared by dissolving NiN and HMT in 200 ml DI water. This
container was placed into the oven held at a constant temperature of 90 C for 6 hours. After the
growth the sample was washed by DI water and dried by nitrogen. After the growth of NiO
nanostructure the sample was ready to be used for preparing low power LEDs. Therefore
structural analysis is essential, so SEM, XRD, C.L and UV techniques were used for the
characterization of the prepared sample. The same steps are followed for the growth of Co 3O4
(cobalt oxide) nanostructure. Hydrothermal technique has large number of advantages over the
other synthesis techniques. It is very easy to handle, consume low power, required small time for
the growth of nanostructure and cheap method.

4. Characterization and Analysis.

Therefore structural analysis is essential, so SEM, XRD, C.L and UV techniques were used for
the characterization of the prepared sample. The same steps are followed for the growth of
Co3O4 (cobalt oxide) nanostructure.X-ray diffraction (XRD) is one of the key methods available
to determine atomic structure, including crystallite size, phase, and phase composition. In order to
investigate the surface morphology of the grown NiO and Co3O4nanostructures scanning electron
microscope technique was employed. Figure 6 is revealing the low and high magnification SEM
images of the morphology of NiO and Co3O4nanostructures grownon glass substrate. It is clear
from Figure 6.1 (a) that NiO nanostructures are looks like honey comb. Beside this they are very
dense and well uniform as shown in figure 6.1 (a)& (b). In addition to this 6.1 (c) & (d) are
showing the morphology of as grown Co3O4nanostructures. The grass like nanostructures of
Co3O4are uniformly distributed all over the substrate and they are interconnected as well.

Advanced Nanoscience and Technology: An Internation al Journal (ANTJ), Vol. 2, No. 1, March 2016

Fig.no. 4: SEM image for NiO nanostructures (a) & (b) and Cobalt Oxide nanostructure (c) & (d)

In order to examine the crystal quality of grown NiO and Co3O4nanostructures XRD
measurements have been performed.The XRD scan (0.1/sec) was performed in the 2 range of
25-70 for NiO and 15-70 for Co3O4nanostructures.Figure 6.2(a) is conforming that NiO
nanostructures are cubic in crystallinity and the presence of rings in nanostructures showing the
nanoflakes nature of NiO. The appearance of Ni (111) reflectionis confirming the presence of
nanocrystalline fcc Ni grains in the prepared sample.The highest appeared peak at (111) and the
peak at (200) of NiO are clearly visible in obtained spectra. The XRD study exhibited the facecentered cubic phase crystalline structure of NiO.The XRD scan showed in Figure 6.2(b)is
revealing the pure phase of Co3O4nanostructures. The XRDspectrum in figure 6.2 (b)is
showingmany peaks related to Co3O4nanostructures. These peaks are in well agreement with
JCPDS card no. 05-0661). A relatively weak peak related to a monoclinic phase of Co3O4 appears
at 38.7 and it corresponds to the (111) plane. The peaks identied as (112) and (1, 1, 3) are
reections forCo3O4. This study has shown that the fabricated nano structure is only composed of
Co3O4materials and the obtained results are consistent with the SEM analysis.

Advanced Nanoscience and Technology: An Internation al Journal (ANTJ), Vol. 2, No. 1, March 2016

Fig.no 5. X Ray diffraction pattern of NiO (a) and Co3O4(b) nanostructure

For the study of luminescence nature of grown NiO and Co3O4nanostructures, UV-vis
spectroscopywas performed at room temperature. Figure 6.3(a) has shown enhanced UV
luminescence at room temperature for NiO nanostructures while Co3O4showed very weak
luminesce in the visible region as shown in figure 6.3(b). We have measured the pure
Co3O4nanostructuresand we have not detected any strong luminesce in the visible region.

Fig.no.6 (a) UV vis spectrum of NiO and (b) UV vis spectrum of Co3O .
5

Advanced Nanoscience and Technology: An Internation al Journal (ANTJ), Vol. 2, No. 1, March 2016

Cathodoluminescentstudy was done in order to confirm luminescein the as grown nanostructures

of NiO and Co3O4. CL spectra are practically independent on the electron beam energy, only a
marginal increase of the relative intensity of the visible emission has been detected. It is clear
from the graph shown by the figure 6.4 that NiO has an intense peak about 500 nm with intensity
of around 1400 a.u.This result proves that NiO nanostructures are good to be used for LEDs.
We have measured the pure Co3O4nanostructures and we have not detected any luminescence in
UV or in the visible region therefore cobalt oxide nanostructure are not suitable for LEDs.

Fig.no 7 : CL spectra of NiO

CONCLUSION
In this study, NiO and Co3O4 nanostructures were fabricated on the glass substrate by employing
aqueous chemical growth method. The structural study of grown nanostructures of NiO and
Co3O4 showed uniform distribution, high density and good crystal quality. Moreover, the NiO
nanostructuresshowed good UV-visible absorption behavior. On the other hand Co3O4
nanostructures have not showed strong UV-visible absorption behavior suitable for LEDs. CL
investigation of NiO nanostructuresshowed the excellent luminescence, but Co3O4nanostructures
did not showed any luminescence in that investigation. This also confirmed the fruitfulness of
NiO and unfruitfulness of Co3O4in the fabrication ofLEDs.

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